High-strength carbon fiber composite material and preparation process thereof

Abstract

The application provides a high-strength carbon fiber composite material and a preparation process thereof, and belongs to the technical field of carbon fiber materials, and comprises the following steps: 3-aminopropyl triethoxysilane is dropped into a hollow glass microsphere suspension, the pH value is adjusted to be acidic, heating and stirring are carried out, the pH value is adjusted, the heating and stirring are carried out after the super-branched polyester amide-ethanol solution is added, vacuum drying is carried out, and a double-modified HGM is prepared; nano-graphene-carbon fiber cloth is soaked in concentrated nitric acid, cleaned, dried, placed in a lanthanum ion modification solution, dried, and a modified carbon fiber cloth is prepared; the modified carbon fiber cloth is infiltrated with an epoxy resin / double-modified HGM suspension, is stacked through a manual layering process, a water absorption pad is laid on the modified carbon fiber cloth after impregnation, a release film is covered, and the whole is wrapped in a vacuum bag, vacuumizing is carried out, molding is carried out, curing is carried out, and a high-strength carbon fiber composite material is prepared. The application can realize high strength and has a certain corrosion resistance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of carbon fiber materials, in particular to a high-strength carbon fiber composite material and a preparation process thereof. BACKGROUND

[0002] As a precision sports equipment, the table surface stiffness and frame stability of a billiard table directly affect the ball hitting accuracy and service life. Although the traditional wooden structure billiard table has a wide range of applications, it has inherent shortcomings: wood is easily deformed by temperature and humidity, and long-term use leads to uneven table surface; the wooden frame is heavy and the overall structural stability is limited, which is difficult to meet the requirements of extreme precision for high-end competitions. In order to improve performance, carbon fiber composite material has become an ideal alternative material due to its high specific strength and high specific modulus, and its potential advantages include significantly reducing weight, greatly improving stiffness and strength, and excellent anti-deformation ability.

[0003] However, when the existing carbon fiber composite material is applied to large structural parts, it still faces several key challenges. First, although carbon fiber itself has strong mechanical properties, due to the existence of certain hydrophobicity and chemical inertness on the surface, the bonding force with the resin matrix is weak, which leads to common interface separation under high load or impact. This separation not only reduces the overall stiffness and strength of the material, but also increases the brittleness of the composite material, which may produce cracks and damage under frequent impact, affecting the service life of the billiard table. In addition, during the forming process of large carbon fiber composite material components, how to effectively avoid defects such as uneven resin flow, bubble residue, and uneven fiber layering is an important technical problem. Especially in the manufacturing process of billiard tables and other components with large structures and high precision requirements, any minor defect can seriously affect the mechanical properties and stability of the material. Bubble, delamination, and porosity problems not only affect the appearance and function of the billiard table, but also may cause deformation, fracture or corrosion during long-term use, which is difficult to meet the requirements of professional training or competition-level billiard tables, as well as other high-stability and precision requirement instruments.

[0004] Therefore, it is necessary to provide a high-strength carbon fiber composite material and a preparation process thereof to solve the problems existing in the prior art. SUMMARY

[0005] Therefore, the present application provides a high-strength carbon fiber composite material and a preparation process thereof, which can achieve high strength while having certain corrosion resistance.

[0006] To achieve the above purpose, the present application provides a preparation process of a high-strength carbon fiber composite material, comprising the following steps:

[0007] S1. 3-Aminopropyltriethoxysilane was dropped into a suspension of hollow glass microspheres, the pH was adjusted to acidic, heated and stirred, the pH was adjusted again, washed, added to a hyperbranched polyesteramide-ethanol solution, heated and stirred, washed, and vacuum dried to obtain dual-modified HGM.

[0008] S2. After soaking the nano-graphene-carbon fiber fabric in concentrated nitric acid, it is washed, dried, immersed in lanthanum ion modification solution, and dried to obtain modified carbon fiber fabric.

[0009] S3. The modified carbon fiber cloth is impregnated with epoxy resin / double modified HGM suspension, and the absorbent pad is placed on the impregnated modified carbon fiber cloth by manually laying it in sequence. Then, the release film is covered and wrapped in a vacuum bag. After vacuuming, it is molded and cured to obtain a high-strength carbon fiber composite material.

[0010] This invention prepares dual-modified hollow glass microspheres (HGM), which improves both the overall strength and the strength and dispersibility of the microspheres at the interface. The hollow glass microspheres can fill the voids between carbon fibers and resin, improving the overall structure of the composite material. They are lightweight and high-strength, reducing the density of the composite material and enhancing its pressure resistance and impact resistance while achieving lightweighting. However, due to their poor dispersibility, agglomerated hollow glass microspheres can form a physical barrier, interfering with the close contact of the reactive functional groups of the resin and curing agent, resulting in a smaller cross-linked network and affecting the overall mechanical strength. By coating the surface of the dual-modified hollow glass microspheres with silane coupling agents and hyperbranching modifiers, the compatibility between the hollow glass microspheres and epoxy resin is enhanced, further improving their dispersibility in the resin. Simultaneously, a dense cross-linked network can be effectively formed, improving the overall mechanical strength. Furthermore, hyperbranched polyesteramide molecules physically adsorbed on the surface of hollow glass microspheres may desorb from the matrix and be released into the epoxy matrix as free hyperbranched polyesteramide molecules. These hyperbranched polyesteramide molecules, due to the presence of numerous hydroxyl groups in their chemical structure, exhibit autocatalytic activity in the curing reaction between the epoxy resin functional groups and the curing agent, thus contributing to a certain degree of plasticization. In addition, the hollow structure of hollow glass microspheres effectively slows down the propagation of sound waves, providing excellent sound insulation. When used as a filler in the production of carbon fiber billiard tables, it can reduce the noise from billiard ball impacts.

[0011] This invention prepares modified carbon fiber cloth, using La in the lanthanum ion modification solution. 3+ La binds to the surface-active groups of carbon fibers through its strong affinity, forming a stable coordination structure. 3+ The 4f orbital provides coordination sites for nonmetallic elements, acting as coordination centers to anchor active groups to the fiber surface, further enhancing the chemical activity of the carbon fiber surface. Furthermore, the uncoordinated La...3+ The lanthanum ion forms a coordination bond with the -OH in the resin, which makes the interface between the resin and other materials more firmly bonded. In addition, the lanthanum ion has strong chemical stability, which further enhances the chemical resistance of the carbon fiber cloth, especially in harsh environments such as humid or corrosive atmospheres, which can effectively inhibit the corrosion process. The multi-level layered structure of graphene in the nanographene-carbon fiber cloth can effectively transfer the load between the matrix and the fiber and reduce stress concentration, further improving the overall strength; in addition, the graphene layer has a higher specific surface area, so that the mixed structure exhibits high porosity and robustness, which is beneficial to ensure the effective penetration of the resin.

[0012] The present application adopts vacuum bag pressure combined with mold forming technology, further removes excess gas and resin in a negative pressure environment, makes the penetration of resin in the carbon fiber cloth more uniform and complete, and compacts the material through the mold pressure to ensure the flatness of the overall carbon fiber layer, while effectively reducing the overflow of resin and preventing delamination and porosity in the composite material; this technology combination can significantly improve the mechanical properties of the composite material, while reducing defects caused by air residues during the forming process.

[0013] The present application adds double modified hollow glass microspheres to the epoxy resin matrix, cooperates with the multi-level layered structure of graphene in the nanographene-carbon fiber cloth, improves the compressive strength and stability of the overall material, avoids the risk of table collapse during use, and the modified carbon fiber cloth and the resin interface are more closely bonded, the addition of lanthanum ions also gives the overall corrosion resistance, adopts vacuum bag pressure combined with mold forming technology, further removes excess gas in a negative pressure environment, ensures that the table maintains good flatness and is not easy to deform, while avoiding the risk of fracture or corrosion in long-term use, therefore the high-strength carbon fiber composite material prepared by the present application can meet the requirements of high-precision competition-level billiard tables, of course, it can also be applied to other high-stability and precision requirement instruments.

[0014] Optionally, the hollow glass microsphere suspension is prepared by mixing an ethanol solution with a volume concentration of 90% and hollow glass microspheres, and then ultrasonic treatment for 45 min.

[0015] Optionally, in step S1, 3-aminopropyltriethoxysilane is added dropwise into the hollow glass microsphere suspension, hydrochloric acid is used to adjust the pH value to 2-3, and then mixed and stirred at 60-80 DEG C for 3-5 h, then sodium hydroxide is used to adjust the pH value to 6-7 and keep for 1-2 h, washed for 3-5 times, added to the hyperbranched polyester amide-ethanol solution, stirred at 70-80 DEG C for 16-24 h, washed for 3-5 times, and vacuum dried at 80 DEG C for 12-16 h to prepare the double modified HGM.

[0016] Optionally, the solvent used in the step S1 is ethanol, the washing times are 3-5 times, and the mass concentration of the hyperbranched polyester amide-ethanol solution is 30%.

[0017] Optionally, the nanographene-carbon fiber cloth is obtained by placing the carbon fiber in a microwave plasma enhanced chemical vapor deposition reaction chamber, vacuumizing to a background pressure of less than 6*10 -3 Torr, then introducing 30sccm of N2 gas, stably increasing the pressure of the reaction chamber to 15Torr, increasing the temperature to 300-600 DEG C under the protection of N2 atmosphere, keeping the N2 flow and applying a microwave excited N2 plasma with a power of 500-950W, etching and pre-treating the surface of the carbon fiber cloth for 2-3min, introducing 20sccm of CH4 gas and keeping the power of the microwave plasma at 500-950W, in-situ growing the graphene nanostructure for 3-4min, then closing the CH4 source, the microwave plasma and the heating system, and obtaining the nanographene-carbon fiber cloth under the constant N2 flow of 50sccm and cooling to room temperature.

[0018] The present application directly grows the graphene nanosheet on the surface of the carbon fiber cloth by using the microwave plasma enhanced chemical vapor deposition, thereby avoiding the problem of poor dispersibility and easy agglomeration of the graphene nanosheet added directly in the matrix.

[0019] Optionally, the lanthanum ion modification liquid is obtained by mixing and stirring ethanol, citric acid, urea and lanthanum chloride for 30-50min.

[0020] In the lanthanum ion modification liquid, the lanthanum ion serves as a coordination center, the citric acid serves as a main ligand, the -COOH / -OH is complexed with La 3+ , active groups are introduced into the carbon fiber, the urea serves as an auxiliary ligand and provides nitrogen-containing groups, the hydroxyl groups generated by the curing agent are dehydrated and condensed with the active groups on the surface of the carbon fiber to improve the interfacial bonding strength, and the mechanical strength of the finally prepared carbon fiber composite material is further improved.

[0021] Optionally, in the step S2, the nanographene-carbon fiber cloth is immersed in concentrated nitric acid with a volume concentration of 60% in a constant-temperature water bath at 50-60 DEG C for 50-80min, washed with distilled water for 3-5 times, dried at 60-80 DEG C for 80-120min, immersed in 200 parts of the lanthanum ion modification liquid for 120-160min, and dried at 80-100 DEG C for 60-120min to obtain the modified carbon fiber cloth.

[0022] The carbon fiber is washed with distilled water to remove the acidic liquid on the surface of the carbon fiber to avoid affecting the subsequent steps.

[0023] The present application improves the roughness of the fiber surface and the number of -OH groups by using concentrated nitric acid in the process of preparing the modified carbon fiber cloth, so as to provide more reaction sites for subsequent lanthanum ion modification, thereby better enhancing the surface activity of the carbon fiber cloth.

[0024] Optionally, the epoxy resin / doubly modified HGM suspension is prepared by mixing bisphenol A type epoxy resin and epoxy curing agent 593, adding the doubly modified HGM, mixing in a magnetic stirrer, and homogenizing with an ultrasonic homogenizer.

[0025] Optionally, the curing temperature in the step S3 is 100-150 DEG C, the time is 2-5h, the water absorption pad is a cotton fiber non-woven fabric or a bamboo fiber non-woven fabric, and the release film is a polytetrafluoroethylene film.

[0026] The present application uses a water absorption pad to remove excess resin and moisture, and uses a release film to avoid resin adhesion on the mold or other surfaces, while ensuring the smoothness of the material surface.

[0027] Optionally, the high-strength carbon fiber composite material comprises the following mass fractions of raw materials: modified carbon fiber cloth 50-60 parts, epoxy resin / doubly modified HGM suspension epoxy resin / doubly modified HGM suspension; the modified carbon fiber cloth comprises the following mass fractions of raw materials: nano graphene-carbon fiber cloth 70-80 parts, lanthanum ion modification liquid 200 parts; the epoxy resin / doubly modified HGM suspension comprises the following mass fractions of raw materials: bisphenol A type epoxy resin 120 parts and epoxy curing agent 593 40-60 parts, and doubly modified HGM 1.5-2 parts.

[0028] The present application adopts the above mass fraction matching ratio, so that the prepared high-strength carbon fiber composite material has high strength and certain corrosion resistance, further improving the overall performance.

[0029] The above technical scheme of the present application at least includes the following beneficial effects:

[0030] 1、The doubly modified hollow glass microspheres in the present application are coated by silane coupling agent and hyperbranched modifier, which improves the bonding force and dispersibility with resin and carbon fiber, effectively improves the structure of the composite material, and enhances the overall strength. While reducing the density, the light weight and high strength characteristics improve the pressure resistance and impact resistance. The self-catalytic effect of hyperbranched polyester amide molecules promotes the curing reaction, enhances the crosslinking network, and has good sound insulation effect, can effectively reduce the billiard ball impact noise, and improve the performance of billiard table.

[0031] 2、The present application uses La 3+The ion enhances the surface chemical activity and interface bonding force of the carbon fiber cloth, the lanthanum ion forms a coordination bond with the -OH group in the resin to improve the corrosion resistance. The multi-level structure of the nano graphene-carbon fiber cloth improves load transfer, reduces stress concentration, and enhances resin permeability through a higher specific surface area to improve overall strength and structural robustness.

[0032] 3、The present application combines vacuum bag pressing and mold pressing forming technology to ensure that the resin uniformly penetrates into the carbon fiber cloth, removes excess gas and resin, and prevents delamination and air holes. The mold pressure compacts the material, improves the mechanical properties of the composite material, reduces defects caused by air residues during the molding process, and improves the overall structure quality. DETAILED DESCRIPTION

[0033] To make the purpose, technical scheme and advantages of the embodiments of the present application clearer, the technical scheme of the embodiments of the present application will be described clearly and completely below in combination with the embodiments of the present application. The described embodiments are part of the embodiments of the present application, and all other embodiments obtained by those of ordinary skill in the art based on the described embodiments of the present application belong to the scope of protection of the present application.

[0034] Embodiment 1

[0035] In 10 parts of a 90% volume concentration ethanol solution, 2 parts of hollow glass microspheres (HGM) were added, and a hollow glass microsphere suspension was prepared by ultrasonic treatment for 45 min; 2 parts of 3-aminopropyltriethoxysilane were added dropwise into the hollow glass microsphere suspension, and the pH value was adjusted to 2 using hydrochloric acid, and after mixing and stirring at 70°C for 4 h, the pH value was adjusted to 7 using sodium hydroxide and maintained for 2 h, and then washed with ethanol 5 times, and then added to 10 parts of a 30% mass concentration hyperbranched polyester amide-ethanol solution, and after stirring at 75°C for 20 h, washed with ethanol 4 times, and then vacuum dried at 80°C for 14 h to obtain double modified HGM.

[0036] 100 parts of carbon fiber cloth were placed in a microwave plasma enhanced chemical vapor deposition reaction chamber, first vacuumed to a background pressure below 6x10 -3 Torr, then 30 sccm of N2 gas was introduced, the pressure of the reaction chamber was stabilized to 15 Torr, the temperature was raised to 400°C under the protection of N2 atmosphere, the N2 flow was maintained and 750W microwave excitation N2 plasma was applied, the carbon fiber cloth surface was etched and pretreated for 3 min, then 20 sccm of CH4 gas was introduced synchronously and the power of the microwave plasma was maintained at 850W, at this time the plasma was changed to CH4 / N2 mixed atmosphere, and the in-situ growth of graphene nanostructure was carried out for 4 min, after the growth was completed, the CH4 gas source, microwave plasma and heating system were turned off, and under the constant N2 flow of 50 sccm, the system was naturally cooled to room temperature, and finally the nano graphene-carbon fiber cloth was obtained.

[0037] Mixing and stirring 240 parts of ethanol, 30 parts of citric acid, 15 parts of urea and 1.5 parts of lanthanum chloride for 40 min to obtain a lanthanum ion modification solution; soaking 80 parts of nanographene-carbon fiber cloth in concentrated nitric acid with a volume concentration of 60% in a constant temperature water bath at 60°C for 70 min, washing the fiber with distilled water for 5 times, drying at 80°C for 80 min, immersing in 200 parts of lanthanum ion modification solution for 160 min, and drying at 80°C for 120 min to prepare a modified carbon fiber cloth.

[0038] After uniformly mixing 120 parts of bisphenol A type epoxy resin and 50 parts of epoxy curing agent 593, 2 parts of double modified HGM are added, mixed in a magnetic stirrer, and homogenized by an ultrasonic homogenizer to prepare an epoxy resin / double modified HGM suspension; after 60 parts of modified carbon fiber cloth is infiltrated with 100 parts of epoxy resin / double modified HGM suspension, the bamboo fiber non-woven fabric is stacked in sequence on the modified carbon fiber cloth after impregnation by a manual lamination process, then a polytetrafluoroethylene film is covered and wrapped in a vacuum bag, the air in the bag is extracted using a vacuum pump to form a negative pressure environment, the composite material in the vacuum bag is placed in a preheated mold for molding, and the high-strength carbon fiber composite material is prepared by curing at 140°C for 3h.

[0039] Example 2

[0040] Add 2 parts of hollow glass microspheres (HGM) to 10 parts of an ethanol solution with a volume concentration of 90%, and prepare a hollow glass microsphere suspension by ultrasonic treatment for 45 min; add 1 part of 3-aminopropyltriethoxysilane to the hollow glass microsphere suspension, adjust the pH value to 3 using hydrochloric acid, mix and stir at 60°C for 3h, adjust the pH value to 6 using sodium hydroxide and maintain for 1h, wash with ethanol for 3 times, add to 5 parts of a hyperbranched polyester amide-ethanol solution with a mass concentration of 30%, stir at 70°C for 16h, wash with ethanol for 3 times, and vacuum dry at 80°C for 12h to prepare double modified HGM.

[0041] Place 80 parts of carbon fiber cloth in a microwave plasma enhanced chemical vapor deposition reaction chamber, first vacuum to a background pressure below 6×10 -3After 30 sccm of N2 gas is introduced, the pressure in the reaction chamber is steadily increased to 15 Torr, and then the temperature is increased to 300°C under the protection of N2 atmosphere. After the N2 flow is maintained and a microwave excitation N2 plasma with a power of 500 W is applied, the surface of the carbon fiber cloth is etched and pretreated for 2 min. Then, 20 sccm of CH4 gas is introduced synchronously, and the power of the microwave plasma is maintained at 500 W. At this time, the plasma is converted into a CH4 / N2 mixed atmosphere, and the in-situ growth of graphene nanostructures is performed for 3 min. After the growth is completed, the CH4 gas source, the microwave plasma, and the heating system are turned off. Under the constant flow of 50 sccm of N2 gas, the composite material is naturally cooled to room temperature. Finally, the nanographene-carbon fiber cloth is obtained.

[0042] A lanthanum ion modification solution is prepared by mixing and stirring 240 parts of ethanol, 30 parts of citric acid, 15 parts of urea, and 6 parts of lanthanum chloride for 30 min. Then, 70 parts of nanographene-carbon fiber cloth is immersed in concentrated nitric acid with a volume concentration of 60% in a constant-temperature water bath at 50°C for 50 min. The fiber is washed with distilled water for 3 times, dried at 60°C for 80 min, and then immersed in 200 parts of the lanthanum ion modification solution for 120 min. Finally, the modified carbon fiber cloth is dried at 80°C for 60 min.

[0043] An epoxy resin / double-modified HGM suspension is prepared by uniformly mixing 120 parts of bisphenol A type epoxy resin and 40 parts of epoxy curing agent 593, adding 1.5 parts of double-modified HGM, mixing in a magnetic stirrer, and homogenizing with an ultrasonic homogenizer. Then, 50 parts of the modified carbon fiber cloth is infiltrated with 100 parts of the epoxy resin / double-modified HGM suspension. Through a manual lay-up process, the cotton fiber non-woven fabric is laid on the modified carbon fiber cloth after impregnation, and then a polytetrafluoroethylene film is covered and wrapped in a vacuum bag. The air in the bag is extracted using a vacuum pump to form a negative pressure environment. The composite material in the vacuum bag is placed in a preheated mold for molding, and cured at 100°C for 2 h. Finally, a high-strength carbon fiber composite material is prepared.

[0044] Example 3

[0045] A hollow glass microsphere (HGM) suspension is prepared by adding 2 parts of HGM to 10 parts of an ethanol solution with a volume concentration of 90% and ultrasonic treatment for 45 min. Then, 1.5 parts of 3-aminopropyltriethoxysilane is added dropwise to the HGM suspension, and the pH value is adjusted to 2.6 using hydrochloric acid. After mixing and stirring at 75°C for 4 h, the pH value is adjusted to 6.2 using sodium hydroxide and maintained for 1.5 h. Then, the HGM is washed with ethanol for 4 times, added to 7 parts of a hyperbranched polyester amide-ethanol solution with a mass concentration of 30%, stirred at 80°C for 24 h, washed with ethanol for 4 times, and vacuum dried at 80°C for 13 h. Finally, double-modified HGM is prepared.

[0046] The 90 parts of carbon fiber cloth are arranged in a microwave plasma enhanced chemical vapor deposition reaction chamber. First, vacuum is extracted to a background pressure below 6x10 -3 Torr, 30 sccm of N2 gas is introduced, the pressure of the reaction chamber is stably increased to 15 Torr, after the temperature is increased to 600 DEG C under the protection of N2 atmosphere, the N2 flow is maintained and 950 W microwave excitation N2 plasma is applied, the carbon fiber cloth surface is etched and pretreated for 2.5 min, 20 sccm of CH4 gas is introduced synchronously and the power of the microwave plasma is maintained at 950 W, at this time the plasma is converted into CH4 / N2 mixed atmosphere, in-situ growth of graphene nanostructure is carried out for 3.5 min, after the growth is completed, the CH4 gas source, microwave plasma and heating system are turned off, under the constant N2 flow of 50 sccm, the temperature is naturally cooled to room temperature, and finally the nanometer graphene-carbon fiber cloth is obtained.

[0047] The 240 parts of ethanol, 30 parts of citric acid, 15 parts of urea and 4.5 parts of lanthanum chloride are mixed and stirred for 50 min to obtain a lanthanum ion modified liquid; 80 parts of nanometer graphene-carbon fiber cloth are soaked in concentrated nitric acid with a volume concentration of 60% in a constant temperature water bath at 60 DEG C for 80 min, the fiber is washed with distilled water for 4 times, dried at 80 DEG C for 120 min, immersed in 200 parts of lanthanum ion modified liquid for 150 min, and dried at 100 DEG C for 120 min to obtain the modified carbon fiber cloth.

[0048] The 120 parts of bisphenol A type epoxy resin and 60 parts of epoxy curing agent 593 are uniformly mixed, 1.6 parts of double modified HGM is added, mixed in a magnetic stirrer, and homogenized by an ultrasonic homogenizer to obtain an epoxy resin / double modified HGM suspension; 55 parts of the modified carbon fiber cloth are infiltrated with 110 parts of the epoxy resin / double modified HGM suspension, then stacked in sequence by a manual lamination process, cotton fiber non-woven fabric is laid on the modified carbon fiber cloth after impregnation, then a polytetrafluoroethylene film is covered and wrapped in a vacuum bag, air in the bag is extracted by a vacuum pump to form a negative pressure environment, the composite material in the vacuum bag is put into a preheated mold for molding, and a high-strength carbon fiber composite material is prepared by curing at 120 DEG C for 3 h.

[0049] Example 4

[0050] In 10 volumes of 90% ethanol solution, 2 parts of hollow glass microspheres (HGM) were added, and a hollow glass microsphere suspension was prepared by ultrasonic treatment for 45 min; 1.7 parts of 3-aminopropyl triethoxysilane was added dropwise into the hollow glass microsphere suspension, and the pH value was adjusted to 3 using hydrochloric acid, and after mixing and stirring at 80°C for 5h, the pH value was adjusted to 6.5 using sodium hydroxide and maintained for 2h, and then washed with ethanol for 5 times, and then added into 9 parts of 30% mass concentration hyperbranched polyester amide-ethanol solution, and after stirring at 80°C for 24h, washed with ethanol for 4 times, and vacuum dried at 80°C for 16h, to obtain double modified HGM.

[0051] 100 parts of carbon fiber cloth were arranged in a microwave plasma enhanced chemical vapor deposition reaction chamber, first vacuumed to a background pressure below 6×10 -3 Torr, then 30 sccm of N2 gas was introduced, and the pressure in the reaction chamber was stabilized to 15 Torr, then the temperature was raised to 400°C under the protection of N2 atmosphere, and the N2 flow was maintained and a 600W microwave was applied to excite N2 plasma, and the carbon fiber cloth surface was etched and pretreated for 3min, then 20 sccm of CH4 gas was introduced synchronously and the power of the microwave plasma was maintained at 600W, at this time the plasma was converted to a CH4 / N2 mixed atmosphere, and the in-situ growth of graphene nanostructure was carried out for 3min, after the growth was completed, the CH4 gas source, microwave plasma and heating system were turned off, and the constant 50sccm N2 flow was used for natural cooling to room temperature, and finally the nanographene-carbon fiber cloth was obtained.

[0052] 240 parts of ethanol, 30 parts of citric acid, 15 parts of urea and 5 parts of lanthanum chloride were mixed and stirred for 40min to obtain a lanthanum ion modified solution; 72 parts of nanographene-carbon fiber cloth was soaked in concentrated nitric acid with a volume concentration of 60% in a constant temperature water bath at 55°C for 70min, washed with distilled water for 4 times, dried at 70°C for 100min, immersed in 200 parts of lanthanum ion modified solution for 130min, and dried at 90°C for 80min to obtain modified carbon fiber cloth.

[0053] 120 parts of bisphenol A type epoxy resin and 45 parts of epoxy curing agent 593 were mixed uniformly, then 1.8 parts of double modified HGM was added, mixed in a magnetic stirrer, and homogenized by an ultrasonic homogenizer to obtain an epoxy resin / double modified HGM suspension; 56 parts of modified carbon fiber cloth was infiltrated with 110 parts of epoxy resin / double modified HGM suspension, then stacked in order by manual layering process, cotton fiber non-woven fabric was laid on the infiltrated modified carbon fiber cloth, then a polytetrafluoroethylene film was covered and wrapped in a vacuum bag, a vacuum pump was used to extract the air in the bag to form a negative pressure environment, the composite material in the vacuum bag was put into a preheated mold for molding, and cured at 120°C for 3.5h to obtain a high-strength carbon fiber composite material.

[0054] Example 5

[0055] In 10 parts of 90% volume concentration ethanol solution, 2 parts of hollow glass microspheres (HGM) were added, and a hollow glass microsphere suspension was prepared by ultrasonic treatment for 45 min; 1.2 parts of 3-aminopropyltriethoxysilane was dropped into the hollow glass microsphere suspension, and the pH value was adjusted to 2.6 using hydrochloric acid, and after mixing and stirring at 70°C for 4 h, the pH value was adjusted to 6.8 using sodium hydroxide and maintained for 1.5 h, and then washed with ethanol for 5 times, and then added to 6 parts of 30% mass concentration hyperbranched polyester amide-ethanol solution, and after stirring at 80°C for 22 h, washed with ethanol for 3 times, and vacuum dried at 80°C for 14 h, to obtain double modified HGM.

[0056] 80 parts of carbon fiber cloth were arranged in a microwave plasma enhanced chemical vapor deposition reaction chamber, first vacuumed to a background pressure below 6x10 -3 Torr, then 30 sccm of N2 gas was introduced, the reaction chamber pressure was stabilized to 15 Torr, under the protection of N2 atmosphere, the temperature was raised to 400°C, then the N2 flow was maintained and 750W microwave excitation N2 plasma was applied, the carbon fiber cloth surface was etched and pretreated for 2 min, then 20 sccm of CH4 gas was introduced synchronously and the microwave plasma power was maintained at 750W, at this time the plasma was converted to CH4 / N2 mixed atmosphere, and the in-situ growth of graphene nanostructure was carried out for 4 min, after the growth was completed, the CH4 gas source, microwave plasma and heating system were turned off, under the constant N2 flow of 50 sccm, the system was naturally cooled to room temperature, and finally the nanographene-carbon fiber cloth was obtained.

[0057] 240 parts of ethanol, 30 parts of citric acid, 15 parts of urea and 4 parts of lanthanum chloride were mixed and stirred for 40 min to obtain a lanthanum ion modification solution; 72 parts of nanographene-carbon fiber cloth were soaked in 60% volume concentration concentrated nitric acid at 60°C in a constant temperature water bath for 60 min, washed with distilled water for 4 times, dried at 70°C for 110 min, immersed in 200 parts of lanthanum ion modification solution for 160 min, and dried at 80°C for 120 min to obtain modified carbon fiber cloth.

[0058] After 120 parts of bisphenol A type epoxy resin and 40 parts of epoxy curing agent 593 are mixed uniformly, 2 parts of double modified HGM are added, mixed in a magnetic stirrer, and homogenized by an ultrasonic homogenizer to prepare an epoxy resin / double modified HGM suspension; after 60 parts of modified carbon fiber cloth are impregnated with 100 parts of the epoxy resin / double modified HGM suspension, the impregnated modified carbon fiber cloth is stacked in sequence by a manual lay-up process, cotton fiber non-woven fabric is laid on the modified carbon fiber cloth, then a polytetrafluoroethylene film is covered and wrapped in a vacuum bag, air in the bag is extracted by a vacuum pump to form a negative pressure environment, the composite material in the vacuum bag is placed in a preheated mold for molding, and the high-strength carbon fiber composite material is prepared by curing at 110°C for 5h.

[0059] Example 6

[0060] After 2 parts of hollow glass microspheres (HGM) are added to 10 parts of an ethanol solution with a volume concentration of 90%, a hollow glass microsphere suspension is prepared by ultrasonic treatment for 45 min; 1 part of 3-aminopropyltriethoxysilane is added dropwise to the hollow glass microsphere suspension, the pH value is adjusted to 2 using hydrochloric acid, and after mixing and stirring at 80°C for 3h, the pH value is adjusted to 6 using sodium hydroxide and maintained for 2h, and then washed with ethanol for 5 times, and then added to 5 parts of a hyperbranched polyester amide-ethanol solution with a mass concentration of 30%, stirred at 70°C for 24h, washed with ethanol for 3 times, and vacuum dried at 80°C for 16h to prepare double modified HGM.

[0061] 100 parts of carbon fiber cloth are placed in a microwave plasma enhanced chemical vapor deposition reaction chamber, first vacuumed to a background pressure below 6x10-3 Torr, then 30 sccm of N2 gas is introduced, the pressure in the reaction chamber is stably increased to 15 Torr, under the protection of N2 atmosphere, the temperature is increased to 300°C, then the N2 flow is maintained and a 500W microwave excitation N2 plasma is applied, the carbon fiber cloth surface is etched and pretreated for 3min, then 20sccm of CH4 gas is introduced synchronously and the power of the microwave plasma is maintained at 500W, at this time the plasma is converted to a CH4 / N2 mixed atmosphere, and the in-situ growth of graphene nanostructure is carried out for 4min, after the growth is completed, the CH4 gas source, microwave plasma and heating system are turned off, and the sample is naturally cooled to room temperature under a constant N2 flow of 50sccm, and finally a nanographene-carbon fiber cloth is obtained.

[0062] Mixing and stirring 240 parts of ethanol, 30 parts of citric acid, 15 parts of urea and 4.5 parts of lanthanum chloride for 30 min to obtain a lanthanum ion modification liquid; soaking 70 parts of nanometer graphene-carbon fiber cloth in concentrated nitric acid with a volume concentration of 60% in a constant temperature water bath at 50°C for 80 min, washing the fiber with distilled water for 3 times, drying at 80°C for 80 min, immersing in 200 parts of lanthanum ion modification liquid for 120 min, and drying at 80°C for 120 min to prepare a modified carbon fiber cloth.

[0063] After uniformly mixing 120 parts of bisphenol A type epoxy resin and 60 parts of epoxy curing agent 593, 1.5 parts of double modified HGM is added, mixed in a magnetic stirrer, and homogenized by an ultrasonic homogenizer to prepare an epoxy resin / double modified HGM suspension; after 60 parts of modified carbon fiber cloth is infiltrated with 120 parts of epoxy resin / double modified HGM suspension, the cotton fiber non-woven fabric is laid on the modified carbon fiber cloth after impregnation by the manual lamination process in sequence, then a polytetrafluoroethylene film is covered and wrapped in a vacuum bag, the air in the bag is extracted by a vacuum pump to form a negative pressure environment, the composite material in the vacuum bag is put into a preheated mold for molding, and the high-strength carbon fiber composite material is prepared by curing at 100°C for 5h.

[0064] The present application also carries out comparative examples and related tests.

[0065] Comparative Example 1

[0066] Compared with Example 1, the only difference is that the double modified HGM is not prepared, and the hollow glass microspheres are directly added, and the other preparation methods and components are completely consistent, and finally the high-strength carbon fiber composite material is prepared.

[0067] Comparative Example 2

[0068] Compared with Example 1, the only difference is that the modified carbon fiber cloth is not prepared, and the nanometer graphene-carbon fiber cloth is directly used, and the other preparation methods and components are completely consistent, and finally the high-strength carbon fiber composite material is prepared.

[0069] Comparative Example 3

[0070] Compared with Example 1, the only difference is that the vacuum bag molding technology is not used, and the molding is directly molded, and the other preparation methods and components are completely consistent, and finally the high-strength carbon fiber composite material is prepared.

[0071] Performance test

[0072] The samples prepared in Examples 1-6 and Comparative Examples 1-3 are tested for performance, and the tensile strength test is carried out according to the national standard GB / T1447-2005 Fiber Reinforced Plastic Tensile Property Test Method;

[0073] The samples prepared in Examples 1-6 and Comparative Examples 1-3 are subjected to bending strength test according to the national standard GB / T 1449-2005 Fiber Reinforced Plastics Bending Properties Test Method;

[0074] The samples prepared in Examples 1-6 and Comparative Examples 1-3 are subjected to density test according to the national standard GB / T 1463-2005 Fiber Reinforced Plastics Density and Relative Density Test Method;

[0075] The samples prepared in Examples 1-6 and Comparative Examples 1-3 are subjected to salt spray test, and the salt spray test conditions are: 35℃, 5% NaCl, pH value of 3.5±0.5, and maintaining for 240h. The surface state and tensile strength retention rate of the samples prepared in Examples 1-6 and Comparative Examples 1-3 after 240h under the above conditions are analyzed to evaluate the corrosion resistance. The specific test results are shown in Table 1.

[0076] Table 1: Performance test table

[0077]

[0078] As shown in Table 1, the mechanical properties and corrosion resistance of the high-strength carbon fiber composite material prepared in Examples 1-6 are significantly better than those of Comparative Examples 1-3, and the density is in the range of 1.5-1.6g / cm 3 , which can achieve lightweight.

[0079] According to the data analysis in Table 1, compared with Comparative Example 1, the addition of the double-modified HGM coated with silane coupling and hyperbranched modifier in Example 1 makes it more uniformly dispersed in the matrix, further significantly improving the mechanical strength and corrosion resistance. Compared with Comparative Example 2, the dense coordination layer formed by the modified carbon fiber cloth obtained by using lanthanum ion modifier in Example 1 enhances the bonding strength with the resin, blocks the penetration of corrosive medium, and also significantly improves the mechanical strength and corrosion resistance. In Comparative Example 3, the vacuum bag molding technology is not used, resulting in uneven resin penetration and significant porosity defects, and the mechanical properties and corrosion resistance also decrease significantly. In summary, the high-strength carbon fiber composite material prepared by the present application has a weight reduction of about 20% compared with the traditional wooden structure, and has extremely high strength and corrosion resistance, which can be applied to prepare high-precision competition-level billiard tables, and of course can also be applied to other high-stability and precision requirement instruments.

[0080] The above is the preferred embodiment of the present application, and those skilled in the art can make some improvements and refinements without departing from the principles of the present application, and these improvements and refinements should also be considered within the protection scope of the present application.

Claims

1. A preparation process for a high-strength carbon fiber composite material, characterized in that, Includes the following steps: S1. 3-Aminopropyltriethoxysilane was dropped into a suspension of hollow glass microspheres, the pH was adjusted to acidic, heated and stirred, the pH was adjusted to 6-7, washed, added to a hyperbranched polyesteramide-ethanol solution, heated and stirred, washed, and vacuum dried to obtain dual-modified HGM. S2. After soaking the nano-graphene-carbon fiber fabric in concentrated nitric acid, it is washed, dried, immersed in lanthanum ion modification solution, and dried to obtain modified carbon fiber fabric. S3. The modified carbon fiber cloth is impregnated with epoxy resin / double modified HGM suspension, and the absorbent pad is placed on the impregnated modified carbon fiber cloth by manually laying it in sequence. Then, the release film is covered and wrapped in a vacuum bag. After vacuuming, it is molded and cured to obtain a high-strength carbon fiber composite material. The nano-graphene-carbon fiber cloth is produced by arranging carbon fibers in a microwave plasma-enhanced chemical vapor deposition reaction chamber, and then evacuating the chamber to a background pressure below 6 × 10⁻⁶. -3 After Torr, N2 gas at 30 sccm is introduced to stabilize the pressure in the reaction chamber to 15 Torr. Under N2 atmosphere protection, the temperature is raised to 300-600℃. While maintaining the N2 flow rate, a microwave-excited N2 plasma at 500-950W is applied to pre-etch the carbon fiber cloth surface for 2-3 minutes. Then, CH4 gas at 20 sccm is introduced and the microwave plasma power is maintained at 500-950W for in-situ growth of graphene nanostructures for 3-4 minutes. Finally, the CH4 gas source, microwave plasma, and heating system are turned off, and the mixture is cooled to room temperature under a constant N2 flow of 50 sccm.

2. The preparation process of a high-strength carbon fiber composite material according to claim 1, characterized in that, The hollow glass microsphere suspension was prepared by mixing a 90% volume concentration ethanol solution with hollow glass microspheres and then ultrasonically treating the mixture for 45 minutes.

3. The preparation process of a high-strength carbon fiber composite material according to claim 1, characterized in that, In step S1, 3-aminopropyltriethoxysilane is dropped into a suspension of hollow glass microspheres, the pH is adjusted to 2-3 using hydrochloric acid, and the mixture is stirred at 60-80°C for 3-5 hours. Then, the pH is adjusted to 6-7 using sodium hydroxide and maintained for 1-2 hours. After washing 3-5 times, the mixture is added to a hyperbranched polyesteramide-ethanol solution, stirred at 70-80°C for 16-24 hours, washed 3-5 times, and vacuum dried at 80°C for 12-16 hours to obtain the dual-modified HGM.

4. The preparation process of a high-strength carbon fiber composite material according to claim 1, characterized in that, In step S1, the solvent used for washing is ethanol, the number of washing cycles is 3 to 5, and the mass concentration of the hyperbranched polyesteramide-ethanol solution is 30%.

5. The preparation process of a high-strength carbon fiber composite material according to claim 1, characterized in that, The lanthanum ion modified solution is obtained by mixing and stirring ethanol, citric acid, urea and lanthanum chloride for 30-50 minutes.

6. The preparation process of a high-strength carbon fiber composite material according to claim 1, characterized in that, In step S2, the nano-graphene-carbon fiber cloth is immersed in a constant temperature water bath at 50-60°C in concentrated nitric acid with a volume concentration of 60% for 50-80 minutes, washed with distilled water 3-5 times, dried at 60-80°C for 80-120 minutes, immersed in 200 parts of lanthanum ion modification solution for 120-160 minutes, and dried at 80-100°C for 60-120 minutes to obtain modified carbon fiber cloth.

7. The preparation process of a high-strength carbon fiber composite material according to claim 1, characterized in that, The epoxy resin / double-modified HGM suspension is prepared by mixing bisphenol A type epoxy resin and epoxy curing agent 593, adding double-modified HGM, mixing in a magnetic stirrer, and homogenizing with an ultrasonic homogenizer.

8. The preparation process of a high-strength carbon fiber composite material according to claim 1, characterized in that, In step S3, the curing temperature is 100~150℃ and the time is 2~5h. The absorbent pad is made of cotton fiber nonwoven fabric or bamboo fiber nonwoven fabric, and the release membrane is a polytetrafluoroethylene membrane.

9. A high-strength carbon fiber composite material, characterized in that, The high-strength carbon fiber composite material is prepared according to any one of claims 1 to 8, comprising the following raw materials in parts by weight: 50 to 60 parts of modified carbon fiber cloth and epoxy resin / double-modified HGM suspension. The modified carbon fiber cloth comprises the following raw materials in parts by weight: 70-80 parts of nano-graphene-carbon fiber cloth and 200 parts of lanthanum ion modifying liquid; the epoxy resin / double-modified HGM suspension comprises the following raw materials in parts by weight: 120 parts of bisphenol A epoxy resin and 40-60 parts of epoxy curing agent 593 and 1.5-2 parts of double-modified HGM.

Images